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EP1179534A1 - Méthode pour le retraitement du résidu obtenu par le procédé direct pour la synthèse d'organosilanes - Google Patents

Méthode pour le retraitement du résidu obtenu par le procédé direct pour la synthèse d'organosilanes Download PDF

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Publication number
EP1179534A1
EP1179534A1 EP01112039A EP01112039A EP1179534A1 EP 1179534 A1 EP1179534 A1 EP 1179534A1 EP 01112039 A EP01112039 A EP 01112039A EP 01112039 A EP01112039 A EP 01112039A EP 1179534 A1 EP1179534 A1 EP 1179534A1
Authority
EP
European Patent Office
Prior art keywords
residues
alkylchlorosilanes
silicon
disilanes
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01112039A
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German (de)
English (en)
Other versions
EP1179534B1 (fr
Inventor
Konrad Dr. Mautner
Bernd Köhler
Gudrun Tamme
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
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Wacker Chemie AG
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Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP1179534A1 publication Critical patent/EP1179534A1/fr
Application granted granted Critical
Publication of EP1179534B1 publication Critical patent/EP1179534B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
    • C07F7/128—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions covered by more than one of the groups C07F7/122 - C07F7/127 and of which the starting material is unknown or insufficiently determined

Definitions

  • the invention relates to a method for producing Alkylchlorosilanes from the liquid components of Residues from the direct synthesis of alkylchlorosilanes.
  • the solids consist of silicon, metal chlorides, e.g. B. AlCl 3 , metal silicides and carbon black.
  • non-cleavable disilanes processes have been developed in which non-cleavable disilanes converted into cleavable disilanes and then cleaved, e.g. described in US 4,393,229, or in which these disilanes directly on special, mostly precious metal-containing catalysts be cleaved with HCl, e.g. B. described in US 5,502,230.
  • the disadvantage of metal-catalyzed reactions is always that Tendency of the catalysts to become poisoned by impurities the backlog.
  • No. 5,877,337 describes a method which also residues of direct synthesis from Process organochlorosilanes at low pressures and the Convert organosilicon fractions into usable silanes can.
  • the goal is achieved through the thermal fission of the Residues of direct synthesis with hydrogen chloride in one Tube reactor with rotating internals at temperatures of 300 - 800 ° C. Due to the rotating movements of the internals Baking from coking or from the solid matter sheared the reactor walls. An overgrowth of the reactor will thereby prevented.
  • this procedure is the highest Technical implementation requirements and is therefore also correspondingly expensive.
  • No. 5,292,912 describes a method for cleaving the high-boiling residue of direct synthesis with HCl and Catalysts such as activated carbon, supported aluminum chloride and Supported platinum or palladium compounds.
  • HCl and Catalysts such as activated carbon, supported aluminum chloride and Supported platinum or palladium compounds.
  • a carrier aluminum oxide, silica, zeolite or activated carbon described.
  • the process can be carried out as Fixed bed process or in the fluidized bed.
  • a disadvantage of the above-mentioned methods is that high expenditure on equipment to solve the coking problem or but the use of special catalysts z. T on Precious metal base, which make the process more expensive.
  • the object was to provide an improved process that also contains solid residues from direct synthesis of alkylchlorosilanes and the organosilicon Can convert shares into usable silanes.
  • the invention relates to a method for producing Alkylchlorosilanes from the liquid components of Residues of the direct synthesis of alkylchlorosilanes, the one Boiling point of over 70 ° C at 1013 hPa and the Contain disilanes, in which the residues with hydrogen chloride and silicon is heated at temperatures of at least 300 ° C at the same time, at least 10% by weight of tri- and / or tetrachlorosilane based on the weight of the formed Alkylchlorosilanes are formed.
  • the method is particularly characterized in that it is easy to carry out and very long reaction times allows.
  • Hydrogen chloride and Si metal become exothermic Reaction a mixture of tri- and tetrachlorosilane prepared.
  • the equilibrium composition of the mixture depends from the reaction temperature.
  • the enthalpy of reaction is used to feed liquid constituents into the reactor of the residues of the direct synthesis of alkylchlorosilanes Heat reaction temperatures, then the cleavage with hydrogen chloride to monosilanes.
  • a mixture is obtained as the product of tri- and tetrachlorosilane as well as changing proportions of Organochlorosilanes, depending on the composition of the liquid components of the residues.
  • the silicon is preferably in the process as a fixed bed or especially present in a fluidized bed.
  • the amount of HCl can be varied and oriented over a wide range in the case of fluidized bed reactors, essentially the minimum amount to maintain the fluidized bed as the lower limit and the excessive dust discharge from the fluidized bed as upper limit, both strongly dependent on the grain size and the geometric relationships of the reactor depends.
  • the amount of HCl is limited by plant technology and economic constraints z. B. by loss of HCl.
  • hydrogen chloride is used, at least the one contained in the residue Disilanes and the tri- and / or tetrachlorosilanes to be formed molar equivalent amount.
  • the residue and the hydrogen chloride can be both preheated and at ambient temperature in be metered into the reactor, the streams being preferred be dosed continuously.
  • the residue can be when heated can also be dosed as a gas-liquid mixture.
  • the cleavage of the disilanes from the liquid constituents of the residues of the direct synthesis of alkylchlorosilanes produces alkylchlorosilanes of the general formula above, in which R denotes a methyl, ethyl, butyl or propyl radical, in particular a methyl radical.
  • R denotes a methyl, ethyl, butyl or propyl radical, in particular a methyl radical.
  • methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, methyldichlorosilane or dimethylchlorosilane are produced.
  • the target product of the direct synthesis of methylchlorosilanes is usually the dimethyldichlorosilane with a boiling point of 70 ° C, usually more than 80% in the raw mixture accumulates and is purified by distillation.
  • the residues of the Direct synthesis with a boiling point above 70 ° C, preferably at least 80 ° C, in particular at least 100 ° C exist partly from monosilanes, e.g. B. ethyl dichlorosilane, Ethylmethyl dichlorosilane, ethyl trichlorosilane or i-propyltrichlorosilane.
  • the proportions can fluctuate widely and are usually less than 10% behind.
  • Disilanes e.g. B.
  • the proportion of disilanes is usually 20-80 %, usually 40 -80%.
  • Other ingredients are Carbosilanes, oligosilanes with ⁇ three silicon atoms, Hydrocarbons and chlorinated hydrocarbons, their Identification and quantification of great difficulty prepare.
  • the proportion of solids can also be up to 10% by weight. This includes in finely or finely divided form z.
  • silicon and silicides contaminated with catalyst and promoter residues, metal chloride mixtures with main components such as AlCl 3 , CaCl 2 , CuCl, and carbon black.
  • the process is preferably carried out in the presence of the solids carried out as these do not interfere with the process.
  • the silicon can be used in ground or lump form become. It is preferably used in excess for manufacture of tri- and / or tetrachlorosilane used. Preferably Silicon continuously replenished.
  • the amount of liquid constituents added to the Residues of the direct synthesis of alkylchlorosilanes oriented both maintaining the necessary temperature in the Reactor and optionally the fluidized bed.
  • the one obtained in the reaction and exiting the reactor Mixture is condensed, possibly from solids exempt and can wholly or partially that in direct synthesis generated silane mixture fed back or separately in Pure substances are separated.
  • the residue e.g. B. metal salts and other solids depend on silicon surfaces and will eventually together with very fine silicon with the reaction gas ejected and in filters or cyclones from the gas stream deposited.
  • the non-fissile parts can also in Reactor remain and are then periodically with the remaining contents of the reactor removed.
  • the in Both cases can be fixed after appropriate treatment Additive in the ceramic industry or as a slag generator be used. With enough metal it can these metals from the solid portion are also worthwhile isolate e.g. B. copper that leached and back in the Material cycle can be traced.
  • the process is preferably carried out at temperatures of at least 400 ° C, in particular at least 450 ° C and at most 1200 ° C carried out.
  • temperatures> 600 ° C in the reactor begins as Competitive reaction to the split also the split off Alkyl groups from silicon and chlorodisilanes and Chlorosilanes such as trichlorosilane or tetrachlorosilane. This Reaction can be exploited to reduce the distillation effort to keep it low to separate the product mixture.
  • the fully continuous mode of operation of the is particularly preferred Reactor in which both the residues and the silicon be added continuously. If necessary, for a current, e.g. Residues or HCl, several dosing points exist distributed over the reactor length.
  • a current e.g. Residues or HCl
  • Example 1 (analogous to US 2,681,355, not according to the invention)
  • the high-boiling residue consisted of 80% disilanes (mixture of 1,1,2,2-tetrachlorodimethyldisilane, 1,1,2-trichlorotrimethyldisilane and 1,2-dichlorotetramethyldisilane, 2% solids and 18% siloxanes and carbosilanes. A more exact classification was difficult due to the large number of by-products.
  • a split silane with the following composition resulted during the test: substance Proportion in split silane [% by weight] dimethylchlorosilane 1 methyldichlorosilane 10 trimethylchlorosilane 2 methyltrichlorosilane 35 dimethyldichlorosilane 32 solids 3 other 17

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicon Compounds (AREA)
EP01112039A 2000-08-10 2001-05-23 Méthode pour le retraitement du résidu obtenu par le procédé direct pour la synthèse d'organosilanes Expired - Lifetime EP1179534B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10039172 2000-08-10
DE10039172A DE10039172C1 (de) 2000-08-10 2000-08-10 Verfahren zum Aufarbeiten von Rückständen der Direktsynthese von Organochlorsilanen

Publications (2)

Publication Number Publication Date
EP1179534A1 true EP1179534A1 (fr) 2002-02-13
EP1179534B1 EP1179534B1 (fr) 2002-09-11

Family

ID=7652053

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01112039A Expired - Lifetime EP1179534B1 (fr) 2000-08-10 2001-05-23 Méthode pour le retraitement du résidu obtenu par le procédé direct pour la synthèse d'organosilanes

Country Status (5)

Country Link
US (1) US6344578B1 (fr)
EP (1) EP1179534B1 (fr)
JP (1) JP3615722B2 (fr)
CA (1) CA2354299C (fr)
DE (2) DE10039172C1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016011993A1 (fr) 2014-07-22 2016-01-28 Norbert Auner Procédé pour la dissociation de liaisons silicium-silicium et/ou de liaisons silicium-chlore dans des monosilanes, des polysilanes et/ou des oligosilanes

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10056194A1 (de) * 2000-11-13 2002-05-29 Solarworld Ag Verfahren zur Entfernung von Aluminium aus Chlorsilanen
DE10336545B3 (de) * 2003-08-05 2005-04-14 Ge Bayer Silicones Gmbh & Co. Kg Verfahren zur Herstellung von Chlorsilanen
DE102006009954A1 (de) * 2006-03-03 2007-09-06 Wacker Chemie Ag Wiederverwertung von hochsiedenden Verbindungen innerhalb eines Chlorsilanverbundes
DE102006053157A1 (de) * 2006-11-10 2008-05-15 Wacker Chemie Ag Verfahren zum Verdampfen von Bestandteilen einer Flüssigkeit
DE102008000410A1 (de) 2008-02-26 2009-08-27 Wacker Chemie Ag Verfahren zur Herstellung von Alkylchlorsilanen aus den Rückständen der Direktsynthese von Alkylchlorsilanen
KR101573933B1 (ko) * 2008-02-29 2015-12-02 미쓰비시 마테리알 가부시키가이샤 트리클로로실란의 제조 방법 및 제조 장치
WO2010065287A1 (fr) * 2008-12-03 2010-06-10 Dow Corning Corporation Procédé de fabrication de trichlorosilane et de tétrachlorosilane
US8476344B2 (en) * 2009-08-18 2013-07-02 Heritage Environmental Services, Llc Method for preparing silicon-sulfur compounds and their use in bitiminous compositions
DE102010061814A1 (de) * 2010-11-23 2012-05-24 Wacker Chemie Ag Verfahren zum Aufarbeiten von flüssigen Rückständen der Direktsynthese von Organochlorsilanen
DE102011005643A1 (de) * 2011-03-16 2012-09-20 Evonik Degussa Gmbh Reaktorkonzept zur Umsetzung von Organochlorsilanen und Siliciumtetrachlorid zu wasserstoffhaltigen Chlorsilanen
DE102011110040B4 (de) * 2011-04-14 2024-07-11 Evonik Operations Gmbh Verfahren zur Herstellung von Chlorsilanen mittels hochsiedender Chlorsilane oder chlorsilanhaltiger Gemische
CN110540206B (zh) * 2018-05-29 2021-05-11 新特能源股份有限公司 流化床反应器的在线排渣装置及在线排渣的方法
CN114258396B (zh) 2019-08-22 2024-09-20 美国陶氏有机硅公司 用于纯化硅化合物的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2681355A (en) * 1953-02-20 1954-06-15 Dow Corning Method of preparing organosilanes
US5877337A (en) * 1997-03-20 1999-03-02 Wacker-Chemie Gmbh Process for preparing alkylchlorosilanes from the residues of direct synthesis of alkylchlorosilanes

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
DE2623290A1 (de) 1976-05-25 1977-12-08 Wacker Chemitronic Verfahren zur herstellung von trichlorsilan und/oder siliciumtetrachlorid
US4393229A (en) 1982-04-28 1983-07-12 General Electric Company Redistribution of polysilanes in high boiling residues
US5292912A (en) * 1993-07-19 1994-03-08 Dow Corning Corporation Catalytic conversion of direct process high-boiling component to chlorosilane monomers in the presence of hydrogen chloride
DE4431995A1 (de) 1994-09-08 1996-03-14 Wacker Chemie Gmbh Verfahren zur Herstellung von wasserstoffhaltigen Methylchlorsilanen
US5627298A (en) * 1996-06-13 1997-05-06 Dow Corning Corporation One step process for converting high-boiling residue from direct process to monosilanes
US5629438A (en) * 1996-09-11 1997-05-13 Dow Corning Corporation Hydrochlorination process for converting high-boiling residue from direct process to monosilanes
FR2777006B1 (fr) * 1998-04-07 2000-08-04 Rhodia Chimie Sa Procede de preparation d'hydrogenosilanes par hydrogenolyse catalytique de polysilanes
US5907050A (en) * 1998-09-30 1999-05-25 Dow Corning Corporation Process for converting polymeric silicon containing compounds to monosilanes
US5922894A (en) * 1998-10-28 1999-07-13 Dow Corning Corporation Process for converting polymeric silicon containing compounds to monosilanes
US6013235A (en) * 1999-07-19 2000-01-11 Dow Corning Corporation Conversion of direct process high-boiling residue to monosilanes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2681355A (en) * 1953-02-20 1954-06-15 Dow Corning Method of preparing organosilanes
US5877337A (en) * 1997-03-20 1999-03-02 Wacker-Chemie Gmbh Process for preparing alkylchlorosilanes from the residues of direct synthesis of alkylchlorosilanes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016011993A1 (fr) 2014-07-22 2016-01-28 Norbert Auner Procédé pour la dissociation de liaisons silicium-silicium et/ou de liaisons silicium-chlore dans des monosilanes, des polysilanes et/ou des oligosilanes
DE102015009129A1 (de) 2014-07-22 2016-01-28 Norbert Auner Verfahren zur Spaltung von Silicium-Silicium-Bindungen und/oder von Silicium-Chlor-Bindungen in Mono-, Poly- und/oder Oligosilanen

Also Published As

Publication number Publication date
CA2354299A1 (fr) 2002-02-10
EP1179534B1 (fr) 2002-09-11
JP2002155089A (ja) 2002-05-28
CA2354299C (fr) 2006-05-16
JP3615722B2 (ja) 2005-02-02
DE10039172C1 (de) 2001-09-13
US6344578B1 (en) 2002-02-05
DE50100025D1 (de) 2002-10-17

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